Phenol and some aliphatic alcohols react with dimethylzinc forming tetramers (MeZnOR),. Some thiols yield insoluble products (MeZnSR),, but t-butylthiol gives pentamers (MeZnSBut), and (EtZnSBut), and isopropylthiol yields a hexamer (MeZnSPr'),. Dimethylamine forms insoluble [ (Me,N),Zn], and no methylzinc compound, but diphenylamine gives the dimer (MeZnNPh,),. Methylzinc acetate and dimethylphosphinate are insoluble and involatile and are considered to be polymeric. All these products disproportionate when heated, evolving dimethylzinc, except (MeZnOBut), which forms isobutene.Reactions are described between many of these compounds and pyridine leading to the formation of monomeric and dimeric complexes containing fourco-ordinate zinc. Infrared data relating to methylzinc groups in 23 complexes are tabulated.REACTIONS between zinc alkyls and various alcohols,l amines,2 and other compounds containing reactive hydrogen have been described, but little was known about the constitution of the zinc-containing products. Compounds resulting from the displacement of only one alkyl group have generally been described as crystalline and soluble in inert solvents, though no molecular-weight data have been reported, and those arising from the loss of both alkyl groups appeared as insoluble, presumably polymeric, materials. The products from diethylzinc and acetoxime provide an example:

Metal-chlorine and -bromine infrared stretching frequencies are reported for a variety of complex halides of zinc, cadmium, and mercury, and for several alkyl-and aryl-mercury halides, including some perfluoro-derivatives. There is no clear relation between v(M-X) and the type of ligand, but frequencies tend to be relatively high in complexes of chelating ligands. Stretching frequencies involving bridging chlorine atoms are considered to be below 200 cm.-l and were not observed. Cadmium-chlorine are lower than mercury-chlorine stretching frequencies in analogous compounds, and it is suggested that in several of the examined cadmium complexes, L,CdCl,, the metal has a distorted-octahedral rather than a tetrahedral environment. Some boronium salts are described which probably contain bridged (M,CI,) 8anions (M = Zn or Cd).INFRARED spectra, in the 2 0 0 4 0 0 cm.-l region in which absorptions due to metalchlorine and metal-bromine stretching vibrations commonly occur, have been reported for a series of tetrahedral complexes MX,2-(M = Mn, Fe, Co, Ni, Cu, or Zn) and for an extensive series of MX,, MX,, and MX, anions2 These absorptions are generally strong and the spectra are relatively simple. They should, therefore, be of considerable diagnostic value, and have, indeed, already been applied to problems in the co-ordination chemistry of tin 3 and some elements of Group VIII.4The value of spectra in this region depends on the availability of data indicating the range of metal-halogen stretching frequencies, and the extent of their dependence on the co-ordination environment of the metal. The aim of the present work is to provide such data for zinc, cadmium, and mercury complexes. Bands due to metal-halogen vibrations could easily be distinguished from those due to the other co-ordinated ligands, for example, by comparing the chloride, bromide and iodide of a given series.Zinc.-Data for thirteen complexes containing the ZnC1, group and eleven containing the ZnBr, group are given in Table 1, together with data for Cs,ZnBr, and a complex containing [ZnC13]-or [Zn2ClJ2-ions. The first point of interest is the small change in v(Zn-X) on passing from the anions ZnX42-to the neutral complexes L,ZnX,. For Cs,ZnCl,, v(Zn-Cl) is at 285 and 292 cm.-l, and is at similar frequencies for (Et4N),ZnCl4 and (Ph,MeA~),2nCl~.~ These are near the lower part of, but inside, the range 277-345 cm.-1 observed for the neutral complexes. For some tin(1v) complexesJ3 v(Sn-C1) is in much the same region for SnCla2-anions (310) as for the complexes py2SnC1, (324) and bipySnC1, (327 and 280 cm.-l). In the neutral zinc bromide complexes, v(Zn-Br) tends

Organoantimony compounds of the type R3SbX and (R,Sb)20X, where R is methyl or phenyl, and X is a bivalent anionic group such as Se04, Cr04, or CzQ4, have been prepared. Structural characteristics of these compounds have been determined by studying their infrared spectra in the solid state between 4000 and 250 cm-I. The spectral results indicate that in both types of conlpounds the anion X is coordinated to the R3Sb or (R,Sb-0-SbR3) group resulting in non-ionic, five coordinate, polymeric structures.

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Notessearch Council of Canada for financial support and the award of a scholarship (to D. R. R.). We are also grateful to Dr. C. J. Willis (University of Western Ontario) for the use of a Cary 82 Raman spectrometer.